Alpha-alkoxyalkylcyanamides and their preparation



United States Patent ABSTRACT OF TIE DISCLOSURE Monomerica-alkoxyalkylcyanamides of the formula where R R and R are hydrogen orlower alkyl and R is alkyl or substituted alkyl of up to 12 carbons. Thecompounds are prepared by reacting cyanogen azide with an ether of theformula RELATED APPLICATIONS This application is a continuation-in-partof my copending application Ser. No. 383,233, filed July 16-, 1964, andmy copending application Ser. No. 215,800, filed Aug. 9, 1962.

FIELD AND DETAILS OF THE INVENTION This invention relates to organiccyanamides and their preparation. More specifically, it concernsmonomeric u-alkoxyalkylcyanamides and certain cyanamido-substitutedpolymeric alkyl ethers and their preparation.

The novel monomeric m-alkoxyalkylcyanamides of the invention arerepresented by the structural formula wherein R R and R separately areeach hydrogen or lower alkyl; R is alkyl of up to 12 carbon atoms orsubstituted alkyl of up to 12 carbon atoms in which the sub- PatentedFeb. 11, 1969 stituents are lower alkoxy, halogen (fluorine, chlorine,bromine, or iodine), cyano, lower alkoxycarbonyl, loweralkylcarbonyloxy, or nitro; R and R taken together represent a divalentalkylene or an oxaalkkylene group of 3-5 carbon atoms; and R and R takentogether represent a divalent alkylene group of 1-4 carbon atoms whichcan be substituted with lower alkoxy.

The novel cyanamido-substituted polymeric alkyl others can be describedas polymeric ethers in which the recurring units are divalentoxaalkylene groups of 1-3 carbon atoms or divalent alkoxyethylene groupsof 3-8 carbon atoms, said polymeric ethers having a cyanamido (NHCN)group attached to 150% of the oz-OXa carbon atoms.

The novel monomeric products are prepared initially by reacting cyanogenazide with an ether of the formula wherein R R and R are defined asabove. The reaction is carried out at temperatures of between about25-150 C. and preferably between 30-75 C. Pressure is not critical andatmospheric, superor subatmospheric pressures can be used in batch,continuous flow, or vapor phase processes.

The process is conducted by simply heating the cyanogen azide with 0.1to equivalents of the ether.

Cyanogen azide is extremely reactive and should not be allowed to dry.It is ordinarily prepared in an inert solvent such as acetonitrile orethyl acetate and placed in the reaction mixture in solution. Or it canbe prepared in situ with the ether as the reaction mixture. Theseprocesses are more fully described in my above-mentioned co-pending US.application Ser. No. 215,800.

The novel monomeric products can be isolated by conventional procedures.Thermally stable products can be distilled under reduced pressure. Thenovel products can also be obtained by chromatography, extraction orcrystallization. Sufliciently pure products for most applications can beobtained by filtering the reaction mixture and removing the excesssolvent or ether.

To obtain products in which R is lower alkyl, the initial product isreacted with a lower alkyl halide in the presence of an alkali metalalkoxide at 30-50" C. The products can be isolated as previouslydescribed.

The novel cyanamido-substituted polymeric alkyl ethers are obtained byreacting cyanogen azide with a polymeric ether having recurrentoxaalkylene units of 1-3 carbon atoms or recurrent alkoxyethylene unitsof 3-8 carbon atoms. The reaction is carried out at temperatures of be-3 tween about 25-15 C. and preferably between 30-75 C. in a medium whichis a solvent for the cyanogen azide and which may or may not be asolvent for the polymeric ether. Pressure is not critical.

The process is conducted by simply heating the cyanogen azide with 0.1to 100 equivalents of the polymeric ether. Inert solvents for cyanogenazide in this process include saturated aliphatic hydrocarbons,halogenated saturated aliphatic hydrocarbons, saturated aliphaticesters, and saturated aliphatic nitriles. Prepresentative polymericalkyl ether reactants include polyformaldehyd (preferably alkyl-cappedhigh molecular weight polyoxymethylene), polyethylene oxide,polypropylene oxide, polydioxolane, and polyvinyl methyl ether.

The following examples serve to illustrate the invention but are notintended to limit it:

Example I A. l-ETHOXYETHYLCYANAMIDE CHs-CH-O 0E5 HN-ON Cyanogen azide,prepared from sodium azide (3.25 g., 0.05 mole) and cyanogen chloride(25 ml.), was diluted with diethyl ether (50 ml.) and heated at 3037 C.for 26 hours, during which time nitrogen (0.038 mole) was liberated.Cyclohexene (8 ml.) was added to destroy any unreacted cyanogen azide.No additional nitrogen was liberated. The reaction mixture was filteredand the volatiles removed from the filtrate at 1 mm./25 C. to give alight tan, mobile oil having an infrared spectrum essentially identicalwith that of l-ethoxyethylcyanamide (Part B, below). This sampleunderwent exothermic self-com densation on standing at room temperature.

B. l-ETHOXYETHYLCYANAMIDE Cyanogen azide (0.25 mole), prepared inacetonitrile to give a total volume of 110 ml., was diluted with diethylether (900 ml.) and heated at reflux temperature (36- 37 C.) for 11hours. Nitrogen was liberated (0.25 mole) and the solution becamecloudy. The reaction mixture was filtered to separate an amorphous solid(2 g.) and the filtrate evaporated to dryness to give a lightstraw-colored mobile oil (23.2 g., 82%). The infrared spectrum of a neatsample showed absorption at 3.1; (NH), 3.4 .1. (CH), 4.5a (CN). 6.23;;(probably impurity), and 8.4-9.5 (CO-C). A sample of this product fromanother preparation distilled at 1, pressure and a pot temperature of63-73 C. with decomposition and/or rearrangement to give a colorlessoil.

A further sample (0.6 mole) prepared as described above, was filteredand the volatiles removed at 1 mm./ 25 C. The heat oil for-medwell-defined crystals when cooled at -78 C. An aliquot of this oil (4.0g.) was dissolved in methylene chloride (50 ml.) and passed through 1bed of Florisil containing a little Darco. The solvent was removed fromthe eluent under reduced pressure to give a nearly colorless oil (3.5g.). The H n.m.r. spectrum of this oil in carbon tetrachloride withtetramethylsilane as internal standard showed a doublet at 13.58 (1H,J=5.9 c.p.s.) assigned to the proton on nitrogen, a symmetrical -linedpattern at 15.345.70 (1H, 1:5.9 c.p.s.) assigned to the single proton oncarbon adjacent to nitrogen and oxygen, a 14-lined pattern at 16.0-6.82(2H) assigned to the methylene protons adjacent to oxygen, a doublet at18.62 (3H, J=5.9 c.p.s.) for one methyl group, and a triplet at 18.82(3H, J=7.3) for the protons of th methyl group attached to the methylenegroup.

4 Example II METHYL-l-ETHOXYETHYLCYANAMIDE AND METHYL-l-METHOXYETHYLCYANAMIDE To a solution of crude l-ethoxyethylcyanamide(11.4 g., 0.1 mole) in ether (150 ml.) was added with stirring andcooling (0-4 C.) sodium methylate (5.5 g., 0.1 m0le) in absolute ethanol(50 ml.). When addition was complete, methyl iodide (15 g., 0.11 mole)was added and the mixture stirred and heated for 2 hours at 40 C. Thereaction mixture was added to either (400 ml.) and filtered. Thefiltrate was washed with water (50 ml.), dried and the ether removedunder pressure to give a light straw-colored oil (11.3 g., 88.5%). Thisoil was distilled in a shortp'ath still at 2, pressure at a pottemperature of 20-40 C. to give a colorless oil (4.6 g.). Analysis byvapor phase chromatography showed this oil to contain at least twocomponents in a ratio of 16:83. The reaction product was combined withthat from a similar run and an aliquot (10.6 g.) separated by vaporphase chromatography on a 3' x annular column packed with 25% SiliconGum Nitrile XE-60 on firebrick (Gas Chrom R) at a temperature of C. anda helium How of 550 cc./min. The fraction collected at a retention timeof 23.3 min. (B.P. l920/0.1,u, n 1.4231, 0.42 g.) was identified asmethyl-(l-methoxyethyl) cyanamide.

Analysis.-Calcd. for C H N O: C, 52.61; H, 8.83; N, 24.54; M.W., 114.Found: C, 52.42; H, 8.83; N, 24.76; M.W., 114 (mass spec.)

The H n.m.r. spectrum on a neat sample was TMSi as internal standardshowed a quadruplet at 15.65 (1H, J=5.80) assigned to the single protonon carbon adjacent to oxygen,'a single peak at 16.69 (3H) for themethoxyl protons, a single peak at 17.21 (3H) for the protons of themethyl group attached to nitrogen and a doublet at 18.90 (3H, J=5.80)for the protons of the methyl group attached to carbon.

The infrared spectrum of a neat sample showed absorption at 3.33, 3.39,3.52, (saturated CH), 4.51 (CN), 7.23, (CCH), and 8.85 1 (CO-C).

A second fraction collected at a retention time of 34.7 min. (B.P.25/0.1u, n 1.4291, 6.42 g.) was shown to bemethyl-(1-ethoxyethyl)cyanamide.

Analysis.-Calcd. for C H N O: C, 56.22; H, 9.44; N, 21.86; M.W., 128.Found: C, 56.03; H, 9.39; N, 22.24; M.W., 128 (mass spec.).

The H n.m.r. spectrum determined on a neat sample with tetramethylsilaneas internal standard showed a quadruplet at 15.55 (1H, J=5.80), assignedto the single proton on carbon adjacent to oxygen, a complex group(13-15 lines) centered at 16.44 (2H) and assigned to the methyleneprotons adjacent to oxygen, a single strong absorption at 17.22 (3H) forthe protons of the methyl group attached to nitrogen, a doublet at 16.68(3H, J=5.80) for the methyl protons attached to the carbon bearing bothnitrogen and oxygen and a triplet at 18.83 (3H, J=6.90) for the methylprotons attached to the methylene group.

Absorption in the infrared spectrum occurred at 3.37, 3.46 (saturatedC-H), 4.53 1 (CN), 7.25 4 (CCH and 8.95,:1. (C-O-C).

Crude l-ethoxyethylcyanamide, when alkylated by this procedure withsodium ethylate as base, gave only methyl l-ethoxyethylcyanamideisolated in 76% yield and distilled to give the pure product in 69%yield.

Example III TETRAHYDR OFURAN-2-CARBAMONITRILE To a solution of cyanogenchloride (29.4 g., 0.43 mole) in tetrahyrofuran 100 ml.) at was addedsodium azide (3.25 g., 0.05 mole). The mixture was warmed slowly to roomtemperature and stirred for 17 hours, during which time nitrogen wasliberated. The reaction mixture was filtered and the filtrate evaporatedto dryness at 1 mm./ 25 C. to give a clear, mobile oil (5.5 g., 98%).The infrared spectrum was essentially the same as that of the distilledproduct described below and shown to consist primarily oftetrahydrofuran-Z-carbamonitrile. This oil formed a salt with silvernitrate.

In a subsequent preparation, cyanogen azide (0.85 mole) dissolved inacetonitrile to a total volume to 275 ml. was diluted with drytetrahydrofuran (2000 ml.) and heated at 3-0-47 C. for 3 hours (thereaction was exothermic above 39 C.), during which time nitrogen (0.84mole) was liberated. The reaction mixture was evaporated to dryness at 1mm./30 C. to give a light strawcolored mobile oil (85.6 g., 90%).

An aliquot of this product (28.8 g.) was diluted with diethyl ether (300ml.) and passed through a 1" bed of Florisil. The eluent was evaporatedto dryness to give an almost colorless, mobile oil (23.7 g.) which wasdistilled in a short-path still at 0.6 and a pot temperature of 64-95 togive four fractions of a colorless oil (16.1 g., r1 1.4581-1.4839). Thelowest boiling fraction contained up to 35.5% nitrogen, but the highestboiling fraction analyzed correctly fortetrahydrofuran-2-carbamonitrile.

Analysis.Calcd. for C H N O: C, 53.56; H, 7.19; N, 24.98; M.W., 112.Found: C, 53.30; H, 6.90; N, 25.35, 25.01; M.W., 128 (cryoscopic inbenzene).

The H n.m.r. spectrum of fraction 2 determined on a neat sample withtetramethylsilane as internal standard gave a broad absorption at 13.85(1H) and three complex groups at 14.61-5.43 (2H), 15.80-6.40 (2H), and17.508.43 (4H).

The infrared spectrum of a neat sample showed absorption at 3.08,u.(NH),3.34, 3.43 3 (saturated CH), 4.46 (CN). 605a (possibly C=O or C=Nimpurities), 9.55 2 (COC).

Example IV N-METHYLTETRAHYDROFURAN-2-CARBAMONITRILE illi.

Crude tetrahydrofuran-2-carbamonitrile (20.5 g., 0.18 mole) wasdissolved in ethanol (100 ml.). The solution was stirred and cooled at02 C. while sodium methylate (10.8 g., 0.2 mole) dissolved in ethanol(100 ml.) was added. When addition was complete, methyl iodide (75 g.,0.53 mole) was added and the mixture stirred at 52- 57 C. for 17 hours.Volatiles were removed from the reaction mixture at 1 mm./ 30 C. and theresidue taken up in methylene chloride (200 ml.) and filtered. Thefilter cake was dissolved in water and extracted with methylenechloride. The dried extract was combined with the filtrate andevaporated to dryness at 1 mm./30 C. to give a mobile, tan oil (18.4 g.,This oil was distilled in a short-path still to give essentially pureN-methyltetrahydrofuran-Z-carbamonitrile (14.4 g., 70%

An aliquot of this oil was further purified by vapor phasechromatography on a 6' x column packed with 20% Silicon Gum NitrileXE-60 on firebrick, 60/80 mesh (Gas Chrom R), at a column temperature of175 C., a preheat temperature of 200 C., and a helium flow of 200cc./min. -T'he colorless oil, collected at a retention time of 36.2min., was distilled (B.P. 24/ 0.111., n 1.4570) and analyzed.

Analysis.-Calcd. for C H N O: C, 57.12; H, 7.99; N, 22.21; M.W., 126.Found: C, 57.16; H, 8.00; N, 22.47; M.W., 129 (cryoscopic in benzene).

The H n.m.r. spectrum determined on a neat sample with TMSi as internalstandard gave a triple (further split) at 15.17 (1H) assigned to thesingle proton on carbon adjacent to nitrogen and oxygen, a distortedsextet at 16.17 (2H) assigned to the methylene group adjacent to oxygen,a single peak at 17.17 (3H) for the protons of the methyl group onnitrogen and a complex pattern at 17.648.63 (4H) for the methyleneprotons most remote from oxygen.

The infrared spectrum of a neat sample showed absorption at 3.37 and3.45 1. (CH), 4.50 4 (CN) and 9.60p (C-OC).

Example V 1,4-DIOXANE-2-CARBAMONITRILE AND N-METHYL1,4-DIOXANE-2-CARBAMONITRILE 1. O N-CN Cyanogen azide (0.27 mole) inacetonitrile ml.) was diluted with dioxane (686 ml.) and heated withstirring at 44-62 C. for 5 hours, during which time nitrogen (0.27 mole)was liberated. One-third of the reaction mixture was evaporated todryness at Ola/25 C. to give a mobile oil (9.72 g., 93.6%). Theremainder of the reaction mixture was cooled to 0-4 C. and sodiumethylate (11.8 g., 0.18 mole) dissolved in absolute ethanol (75 ml.)added slowly with stirring. When addition was complete, the mixture wasstirred at 0 for 10 min. Methyl iodide (52 g.) was added and thereaction mixture heated at 65-70 C. for 6 hours. The mixture wasfiltered and the filtrate evaporated to dryness under reduced pressure.The residue was taken up in methylene chloride, filtered and thefiltrate evaporated to dryness to give a mobile brown oil (16.2 g.).This oil was distilled in a molecular still at 0.04 3 pressure and a pottemperature of 30-105 C. to give a colorless oil (6.79 g.). A sampleprepared in this way was purified by vapor phase chromatography 011 a 3'column packed with 25% Silicone Gum Nitrile XE-60" on firebrick at atemperature of C. and a helium flow of 430 cc./ min. The samplecollected at a retention time of 55.7 min. was distilled (BJP. 35-37C./0.01/.L, n 1.4660) and was shown to beN-methyl-l,4-dioxane-Z-carbamonitrile.

Analysis.-Calcd. for G l-1 N 01 C, 50.69; H, 7.09; N, 19.71; M.W., 142.Found: C, 50.33, 50.35; H, 7.05, 6.99; N, 19.9; M.W., 147 and 148(cryoscopic in benzene).

The H n.m.r. spectrum determined on a neat sample with tetramethylsilaneas internal standard showed a single sharp absorption at 17.08 (3H)assigned to the methyl protons and a typical A-B-C-type pattern for theremaining protons including two doublets at 15.60 and 15.71 (1H)assigned to the single proton on carbon adjacent to oxygen and a 14-linepattern at 1590-680 (6H) assigned to the remaining methylene protons.

The infrared spectrum showed absorption at 3.37 3.44 3.50; (saturatedC--H), 4.52;, '(CN), and multiple peaks in the 9 region (cyclic CO--C)The following table lists additional ether reactants and thecorresponding products obtained by the general processes described inthe examples:

Ethers Products Methyl-n-butyl ether C H; 0-0 H(C Hz) 1011;l-methoxybutylcyanamide.

NHC N C HzO-(C H2) at 0 Ha B utoxymethylcyanamide;

HN C N Methyl-t-butyl ether O Hz-O C (0 H3) tert.-Butoxymethyleyanamlde.

HN-C N Methylcyclopentyl ether C H3-0 l C Hr-O HN oN NEONl-methoxyeyelopent ane-l-carbamonitrlle Cyelopentoxymethyleyanamlde.

Ethyl-n-heptyl ether C H3C H0 (0 H1) 6-0 H3 l-heptoxyethyleyanamide;

HN C N C Ha-C Hz-O C H-(O Hz) 0 H l-ethoxyheptylcyanamide.

NH O N Isoamyl ether (0 Ha) 2-0 HC HzC H-0 (0 Hz) r-C H 0 Hz)1isopent0xy-3-methylbutylcyanamide.

NH O N Isopropyl ether (0 H3) 30 ---O% (0 Hz) a l-isoprop oxy-l-methylethyleyanamide.

EN 0 N Tetrahydropyran H Tetrahydropyran-Z-earbamonltrite.

O N-ON Methyl-a-furyl ether l Z-X'uryloxymethyleyananflde.

o O ('3 H2 N HG N fi o N 2-methoxytetrahydroiuran-2-carbamonitrile.

O to 0 Ha NC-Elo i0 0 H; 5-methoxytetrahydrofuran-2-earbamonitrile;

NHC N Z-methoxytetrahydrofuran-B-earbamonltrile. L O J O 0 Ha Ethyleneoxide 0 Hz@ HNH C N Oximue-Zearbamonltrile.

Tetramethylene oxide C H;C H-NH O N Oxetane-Marbamonltrile.

Dimethyl ether of ethylene glycol C H;0C H-C Hz0 II;LZ-dimethoxyethyleyanamide.

EN 0 N GIL-O-C 11 C H10 CH; Methoxyethoxymethylcyanamide. I iN-C N Ethyln-pentyl ether of ethylene glycol".-. 0 H36 H-O C H10 H; 0(C H9 0 H1-(pentoxyethoxy)ethyleyanamide.

EN 0 N 0 H3O H; 0 O H-C Hr-O (C 1194C Ha1-ethoxy-2-pentoxyethyleyanamide.

EN 0 N l-pentoxy-Z-ethoxyethylcyanmnlde.

1-(ethoxyethoxy)pentylcyanamide.

Ethers Products Chloromethyl ethyl ether C Ha-O-CH2C H;1-(ehloromethoxy)ethyleyanamide.

l N H-CN E Bromomethyl, Z-butyl ether C Hr-O C H20 Ha l-methyl-l-(brornomethoxy)propylcyana.rnide:

Br NH C N Cl 2,3-dichlorotetrahydropyran H5,6-dichlorotetrahydropyran-2-carbamonitrile.

Cl N CN a-Cyanotetrahydrofuran l I H-cyanotetrahydrofuran-Z-carbamonitrile.

N C \O/ C N Methyl B-methoxypropionate 01330 C H-C HzC-O C H;

NHCN

ll CHz-OCBzOHzC-OCHa O l Methyl ether of ethylene glycol monoacctate 0 H0-0 H C H: 0 (i-C Ha O I CHa-O CHzCH2OCHa5-cyanomethyltetrahydrofuran-2-carbamonitrile.

l-methoxy-2-(methoxycarbonyl)-ethylcyanamidnMethoxycarbonylethoxy-methylcyanemide;

1-methoxy-2-acetoxyethylcyanamlde.

Acetoxyethoxymethylcyanamide.

HNCN

MethyI-Z-nitroethyl ether CHz-OCHz-CH2 2-nitroethoxymethylcyanamide.

NHON NO:

0 H3- 0 C H-O HzN O l-methoxy-2-nitroethylcyanamide.

HN-CN Example VI Low-molecular-weight monomeric a-alkoxyalkylcyan- 45amides are usually water-soluble, mobile oils which self- PRODUCTS FROMPOLYOXYMETHYLENE AND CYANOGEN AZIDE Samples of alkyl-cappedpolyoxymethylene were suspended in ethyl acetate (circa ml./ g. ofpolymer), portions of 1.2 to 2.0 molar cyanogen azide in ethyl acetatewere added, and the mixtures were heated under reflux for 2 to 3 hours.The yellow solid products were separated by filtration and then treatedwith boiling water which removed the yellow color and converted pendentcyanamido (-NHCN) groups to corresponding carbamido (NHCONH groups.Films of the resultant products showed infrared absorption at 1670 to1600 cmr indicative of amide substituents (absent in the originalpolyoxymethylene). Additional data are given in the following 60 forwhich the theoretical nitrogen analysis is 31.82%. 75

condense spontaneously on heating at -150 C. to give high-meltingsolids. Higher-molecular-weight monomeric a-alkoxyalkylcyanamides aremore stable and frequently crystalline solids. These cyanamides aremildly acidic and will react with silver nitrate, metal alkoxides orsodium hydride to give salts. These salts are readily alkylated oracetylated to give stable N-acyl or N-alkyl derivatives which arereadily hydrolyzed to the corresponding ureas.

The monomeric compounds of this invention may be 5 dissolved ordispersed in water or organic solvents such as acetone, benzene, methylethyl ketone or alcohols, to form stable solutions or dispersions. Thesesolutions or dispersions may be applied to fibers or fabrics such ascotton broadcloth, Orlon, Dacron, or nylon and the fabric heated at -150C. to give materials which tend to retain the preformed shape. Thesecompounds are thus useful for forming shaped articles of fi'bers orfabrics as demonstrated in the following example:

Example A Cotton broadcloth, Orlon, Dacron, and nylon fabrics wereimmersed in a solution of l-ethoxyethylcyanamide (1 g.) dissolved inwater (4 g.). The fabrics were air-dried and then heated at C. for 1hour. Additional samples of these fabrics were treated in the same waywith the neat compound, and other samples with a solution ofl-ethoxyethylcyanamide (1 g.), in methyl ethyl ketone (2 g.), Fabricstreated with the neat compound or the methyl ethyl ketone solution werestiff and tended to retain a preformed shape. Those treated with thewater solution were not appreciably stiffened but tended to retain ashape when formed, for example, by pressing with a hot iron.

In addition, the novel compounds of the invention can be converted tocorresponding substituted ureas for use in usual urea applications. Thisconversion process is illustrated in the following examples:

Example B 1-(1-ETHOXYETHYL)-1-METHYLUREA A solution ofmethyl-(l-ethoxyethyl)cyanamide (6.0 g., 0.047 mole) in acetone (54 ml.)was cooled in ice and 30% hydrogen peroxide (30 cc.) added at a rate tokeep the temperature at -8 C. Aqueous 10% sodium carbonate (30 ml.) wasadded slowly to maintain the same temperature. When addition wascomplete, the mixture was warmed slowly to room temperature and stirredfor 24 hours. Volatiles were removed at 1 mm./30 C. and the productslurried with absolute ethanol (50 ml.) and again evaporated to drynessunder reduced pressure to give -a white solid (12.4 g.). This solid wasextracted with hot acetone (200 ml.) and the extract evaporated todryness and then sublimed at 100-105 C. and 0.1 1. pressure to give awhite, crystalline solid (6.40 g., 93.5%, M.-P. 76-82). A sample wasrecrystallized from carbon tetrachloride and petroleum ether (M.P.87.888.8) and identified as 1-( l-ethoxyethyll-methylurea)Analysis.Calcd. for C H N O: C, 49.30; H, 9.65; N, 19.16; M.W., 146.Found: C, 49.30; H, 9.55; N, 19.22; M.W., 141 (cryoscopic indimethylsulfoxide).

The H n.m.r. spectrum determined in deuterochloroform withtetramethylsilane as internal standard gave a quadruplet at 14.61distorted by an underlined singlet centered at 14.48 (combined weight.3H). When deuterium oxide was added, the peak at -r4.48 shifted leavinga clean quadruplet (]=6.0 c.p.s.) assigned to the single proton oncarbon adjacent to oxygen. The exchangeable peak was assigned to theamide protons. A multiplet (8 lines) centered at -r6.59 (2H) wasassigned to the methylene protons adjacent to oxygen. A single sharpabsorption at 17.76 (3H) was assigned to the protons of the methyl groupattached to nitrogen. A doublet at 1872 (J=6.0 c.p.s.) and an overlyingtriplet at 78.82 (1:7.0 c.p.s.) having a combined weight equivalent tosix protons were assigned to the methyl groups attached to the carbonbearing both nitrogen and oxygen and the OCH groups, respectively. Theinfrared spectrum showed absorption at 3.0, 3.14;]. (NH 3.36, 3.41 and3.47 1. (saturated CH). 6.04 and 6.26 1. (h0), 7.23n (CCH and multiplebands at 9-9.5,u. region for ether-oxygen absorption.

Example C 1-TETRAHYDROFURYL-l-METHYLUREA To solution ofN-methyltetrahydrofuran-Z-carbamonitrile (5.0 g., 0.04 mole) in acetone(50 ml.) was added hydrogen peroxide (30% aqueous solution, 27 ml.) at08 C. with stirring. A 10% sodium carbonate solution (27 ml.) was thenadded at 010 C., and when the exothermic reaction subsided the mixturewas warmed to room temperature and stirred for 17 hours. Volatiles wereremoved in a rotary evaporator at 0.5 mm./25 C. to give a white solid(9.75 g.). The dry solid was extracted with hot acetone (200 ml.) andthe solvent removed from the extract to give a white, crystalline solid(5.65 g., 99%). An analytical sample was recrystallized from carbontetrachloride, dissolved in methylene chloride and decolorized withcarbon black and then recrystallized twice from ethyl acetate to givewhite needles (M.P. 92.493.4 C.).

Analysis.-Calcd. for C H N 0: C, 49.98; H, 8.39; N, 19.43; M.W., 144.Found: C, 40.09; H, 8.23; N, 19.70, 19.20; M.W., 141 (cryoscopic indimethylsulfoxide).

The H n.m.r. spectrum determined in deuterochloro form withtetramethylsilane as internal standard gave a distorted triplet centeredat 14.5 (1H assigned to the single proton on carbon adjacent to oxygenand nitrogen, a broad absorption at 14.54 (2H) for protons on nitrogen,a weak, strong, strong, weak absorption (further split) at r615 (2H)assigned to the methylene protons adjacent to oxygen, a single peak at17.22 (3H) for the protons of the methyl group on nitrogen, and acomplex absorption at -r7.83-8.32 (4H) for the two methylene groups mostremote from oxygen.

The infrared spectrum showed absorption at 2.96, 3.02, 3.13 and 622 (NH3.39, 3.51 (saturated CH), 6.06 C=O), and 9.60 (COC).

The cyanamido-substituted polymeric alkyl ethers retain the normalusefulness of such polymeric ethers and are enhanced in versatility ofuse by reactivity at the cyanamido sites. For example, the cyanamidogroups can be hydrolyzed in hot water to corresponding urea groups, thusproviding sites for anchoring dyes or for curing by crosslinking.

The foregoing detailed description has been given for clearness ofunderstanding only and no unnecessary limitations are to be understoodtherefrom. The invention is not limited to the exact details shown anddescribed, for obvious modifications will occur to those skilled in theart.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows.

I claim:

1. A compound having the structural formula wherein:

R R and R separately, are each hydrogen or lower alkyl, not more thanone of R and R being hydrogen;

R separately, is alkyl of up to 12 carbon atoms or substituted alkyl ofup to 12 carbon atoms in which the substituent is lower alkoxy, halogen(fluorine, chlorine, bromine or iodine), cyano, lower alkoxycarbonyl,lower alkylcarbonyloxy, or nitro;

R and R taken together, are a divalent alkylene or an oxaalkylene groupof 35 carbon atoms; or

R and R taken together, are a divalent alkylene group of 1-4 carbonatoms which is (1) unsubstituted or (2) substituted with lower alkoxy.

2. The compound of claim 1 wherein R is ethyl, R is methyl, and R and Rare hydrogen, l-ethoxyethylcyanamide.

3. The compound of claim 1 wherein R is ethyl, R and R are methyl, and Ris hydrogen, methyl-1-ethoxyethylcyanamide.

4. The compound of claim 1 wherein R and R joined together are alkyleneof 3 carbon atoms, and R and R are hydrogen,tetrahy-drofuran-Z-carbamonitrile.

5. The compound of claim 1 wherein R and R joined together are alkyleneof 3 carbon atoms, R is hydrogen, and R is methyl,N-methyltetrahydrofuran-Z-carbamonitrile.

3,427,323 13 14 6. The compound of claim 1 wherein R and R joined OTHERREFERENCES to ether are CH CH O-CH and R and R are hygdrogen,1Mioganeagbamonigrfle. Chemlcal Abstracts, vol. 21, pp. 898-99 1927 ab-7. The compound of claim 1 wherein R and R joined fact of Tra'llbe etarticletogether are CH -CH OCH R is hydrogen,

5 HENRY R. JILES, Primary Examiner.

and R is methyl.

References Cited H. I. MOATZ, Assistant Examiner.

UNITED STATES PATENTS US. C1.X.R.

2,331,670 10/1943 Eric-ks et a1. 260551 10 3,108,097 10/1963 Ugi.260-333, 345.1, 345.7, 345.8, 347.3, 347.7, 348, 465.5, 482, 490, 551,553, 67; 8-115.5, 116 .2; 2.60--345.1, 490, FOREIGN PATENTS 345 91,028,967 7/1960 Germany. 15

